diff --git a/src/libs/WorkflowUtils.ts b/src/libs/WorkflowUtils.ts
index 61f784d8f2283..bd81db204418c 100644
--- a/src/libs/WorkflowUtils.ts
+++ b/src/libs/WorkflowUtils.ts
@@ -574,6 +574,23 @@ function getOpenConnectedToPolicyBusinessBankAccounts(bankAccountList: BankAccou
     });
 }
 
+/**
+ * Filter out members who are already assigned to a non-default approval workflow.
+ * This prevents them from appearing in the "Expenses from" picker when creating a new workflow.
+ */
+function filterAvailableMembersForNewWorkflow(approvalWorkflows: ApprovalWorkflow[], availableMembers: Member[]): Member[] {
+    const membersInExistingWorkflows = new Set<string>();
+    for (const workflow of approvalWorkflows) {
+        if (workflow.isDefault) {
+            continue;
+        }
+        for (const member of workflow.members) {
+            membersInExistingWorkflows.add(member.email);
+        }
+    }
+    return availableMembers.filter((member) => !membersInExistingWorkflows.has(member.email));
+}
+
 /**
  * Combine workflow members with available members, deduplicating by email.
  */
@@ -587,6 +604,7 @@ export {
     calculateApprovers,
     convertPolicyEmployeesToApprovalWorkflows,
     convertApprovalWorkflowToPolicyEmployees,
+    filterAvailableMembersForNewWorkflow,
     getApprovalLimitDescription,
     getEligibleExistingBusinessBankAccounts,
     getOpenConnectedToPolicyBusinessBankAccounts,
diff --git a/src/pages/workspace/workflows/WorkspaceWorkflowsPage.tsx b/src/pages/workspace/workflows/WorkspaceWorkflowsPage.tsx
index e9ffc40bf3ea9..713dd40fc865c 100644
--- a/src/pages/workspace/workflows/WorkspaceWorkflowsPage.tsx
+++ b/src/pages/workspace/workflows/WorkspaceWorkflowsPage.tsx
@@ -51,7 +51,7 @@ import {
 } from '@libs/PolicyUtils';
 import {hasInProgressVBBA} from '@libs/ReimbursementAccountUtils';
 import tokenizedSearch from '@libs/tokenizedSearch';
-import {convertPolicyEmployeesToApprovalWorkflows, getEligibleExistingBusinessBankAccounts, INITIAL_APPROVAL_WORKFLOW} from '@libs/WorkflowUtils';
+import {convertPolicyEmployeesToApprovalWorkflows, filterAvailableMembersForNewWorkflow, getEligibleExistingBusinessBankAccounts, INITIAL_APPROVAL_WORKFLOW} from '@libs/WorkflowUtils';
 import type {WorkspaceSplitNavigatorParamList} from '@navigation/types';
 import AccessOrNotFoundWrapper from '@pages/workspace/AccessOrNotFoundWrapper';
 import ExpenseReportRulesSection from '@pages/workspace/rules/ExpenseReportRulesSection';
@@ -100,6 +100,8 @@ function WorkspaceWorkflowsPage({policy, route}: WorkspaceWorkflowsPageProps) {
         localeCompare,
     });
 
+    const availableMembersForNewWorkflow = useMemo(() => filterAvailableMembersForNewWorkflow(approvalWorkflows, availableMembers), [approvalWorkflows, availableMembers]);
+
     const hasValidExistingAccounts = getEligibleExistingBusinessBankAccounts(bankAccountList, policy?.outputCurrency, true).length > 0;
 
     const isAdvanceApproval = (approvalWorkflows.length > 1 || (approvalWorkflows?.at(0)?.approvers ?? []).length > 1) && isControlPolicy(policy);
@@ -158,7 +160,7 @@ function WorkspaceWorkflowsPage({policy, route}: WorkspaceWorkflowsPageProps) {
     const addApprovalAction = useCallback(() => {
         setApprovalWorkflow({
             ...INITIAL_APPROVAL_WORKFLOW,
-            availableMembers,
+            availableMembers: availableMembersForNewWorkflow,
             usedApproverEmails,
         });
 
@@ -174,7 +176,7 @@ function WorkspaceWorkflowsPage({policy, route}: WorkspaceWorkflowsPageProps) {
         }
 
         Navigation.navigate(ROUTES.WORKSPACE_WORKFLOWS_APPROVALS_EXPENSES_FROM.getRoute(route.params.policyID));
-    }, [policy, route.params.policyID, availableMembers, usedApproverEmails]);
+    }, [policy, route.params.policyID, availableMembersForNewWorkflow, usedApproverEmails]);
 
     const filteredApprovalWorkflows =
         policy?.approvalMode === CONST.POLICY.APPROVAL_MODE.ADVANCED || policy?.approvalMode === CONST.POLICY.APPROVAL_MODE.DYNAMICEXTERNAL
diff --git a/tests/unit/WorkflowUtilsTest.ts b/tests/unit/WorkflowUtilsTest.ts
index 8c32b0cc0a307..794ed8fd7747a 100644
--- a/tests/unit/WorkflowUtilsTest.ts
+++ b/tests/unit/WorkflowUtilsTest.ts
@@ -4,6 +4,7 @@ import {
     calculateApprovers,
     convertApprovalWorkflowToPolicyEmployees,
     convertPolicyEmployeesToApprovalWorkflows,
+    filterAvailableMembersForNewWorkflow,
     getApprovalLimitDescription,
     getOpenConnectedToPolicyBusinessBankAccounts,
     mergeWorkflowMembersWithAvailableMembers,
@@ -1006,6 +1007,60 @@ describe('WorkflowUtils', () => {
         });
     });
 
+    describe('filterAvailableMembersForNewWorkflow', () => {
+        it('Should return all members when there are no non-default workflows', () => {
+            const availableMembers = [buildMember(1), buildMember(2), buildMember(3)];
+            const workflows = [buildWorkflow([1, 2, 3], [1], {isDefault: true})];
+
+            const result = filterAvailableMembersForNewWorkflow(workflows, availableMembers);
+
+            expect(result).toEqual(availableMembers);
+        });
+
+        it('Should filter out members already in a non-default workflow', () => {
+            const availableMembers = [buildMember(1), buildMember(2), buildMember(3)];
+            const workflows = [buildWorkflow([1, 2, 3], [1], {isDefault: true}), buildWorkflow([2], [4])];
+
+            const result = filterAvailableMembersForNewWorkflow(workflows, availableMembers);
+
+            expect(result).toEqual([buildMember(1), buildMember(3)]);
+        });
+
+        it('Should filter out members from multiple non-default workflows', () => {
+            const availableMembers = [buildMember(1), buildMember(2), buildMember(3), buildMember(4)];
+            const workflows = [buildWorkflow([1, 2, 3, 4], [1], {isDefault: true}), buildWorkflow([1], [5]), buildWorkflow([3], [6])];
+
+            const result = filterAvailableMembersForNewWorkflow(workflows, availableMembers);
+
+            expect(result).toEqual([buildMember(2), buildMember(4)]);
+        });
+
+        it('Should return all members when workflows list is empty', () => {
+            const availableMembers = [buildMember(1), buildMember(2)];
+
+            const result = filterAvailableMembersForNewWorkflow([], availableMembers);
+
+            expect(result).toEqual(availableMembers);
+        });
+
+        it('Should return empty array when all members are in non-default workflows', () => {
+            const availableMembers = [buildMember(1), buildMember(2)];
+            const workflows = [buildWorkflow([1, 2], [3])];
+
+            const result = filterAvailableMembersForNewWorkflow(workflows, availableMembers);
+
+            expect(result).toEqual([]);
+        });
+
+        it('Should return empty array when available members list is empty', () => {
+            const workflows = [buildWorkflow([1], [2])];
+
+            const result = filterAvailableMembersForNewWorkflow(workflows, []);
+
+            expect(result).toEqual([]);
+        });
+    });
+
     describe('getOpenConnectedToPolicyBusinessBankAccounts', () => {
         const matchingBankAccountID = 12345;